Froth flotation method for recovery of minerals by means of alkali or ammonium alkyl alkylaryl, and aryl sulfinates as froth flotation reagents

ABSTRACT

A froth flotation method for the recovery of mineral values of iron, zinc, copper, and thorium, from their ores, which comprises adding to a water suspension of finely divided ore at a pH from 5 to 9 of alkali or ammonium alkyl, alkylaryl, or aryl sulfinate as promoter-collector; aerating the pulp of the mineral slurry and recovering the floated mineral from the suspension.

[ June 17, 1975 United States Patent [1 1 Petrovich 1 FROTH FLOTATION METHOD FOR RECOVERY OF MINERALS BY MEANS OF ALKALI OR AMMONIUM ALKYL ALKYLARYL, AND ARYL SULFINATES AS F ROTH FLOTATION REAGENTS [76] Inventor: Vojislav Petrovich, 1925 W. Schiller St. Chicago, 111. 60622 [22] Filed: June 12, 1974 [21] Appll l\'o.: 478,380

[52] US. Cl 209/166; 209/106 [51] Int. (ll. 803D l/02 [58] Field of Search 209/166, 167

[56] References Cited UNITED STATES PATENTS 1,182,890 5/1916 Bradford 209/166 1.629.080 5/1927 Laist 209/166 l647,793 11/1927 Burnett 209/166 1678,31] 7/1928 Adam 209/166 1902839 3/1933 Cunningham.... 209/166 2,439,200 4/1948 Booth 209/166 3,122,500 2/1964 Gullctt 209/166 Primary ExaminerRobert Halper [57] ABSTRACT 7 Claims, No Drawings FROTH FLOTATION METHOD FOR RECOVERY OF MINERALS BY MEANS OF ALKALI OR AMMONIUM ALKYL ALKYLARYL, AND ARYL SULFINATES AS FROTI-l FLOTATION REAGENTS It is a prime objective of this invention to provide a method for the beneficiation of hematite and magnetite ores, as the most appreciated metallurgical raw material for iron production, by means of froth flotation method, which will permit a greater and more economical recovery of iron values from their most vast and the most valueless orebody. The present invention point to a cheap, technically accessible, and reliable method for concentration of iron oxide ores to marketable product. Therefore, one of the objectives of the present invention is to provide a simple, expedient, and inexpensive method for the concentration of iron minerals, such as hematite and magnetite by means of alkali or ammonium alkyl, alkylaryl, or aryl sulfinates.

Another prime objective of this invention is to provide a simple, expedient, and inexpensive method for the concentration of zinc minerals from complex sulfidic and oxidic ores, or from oxidized lead, zinc, copper, pyrite ores, by means of alkali and ammonium alkyl, alkylaryl or aryl sulfinates as a new class of froth flotation reagents which are particularly adapted for application in a highly selective method for the recovery of zinc minerals from complex sulfidic and oxidic ores.

Accordingly, a principal objective of this invention is to provide a new class of froth flotation reagents for iron oxide minerals, as well as oxide, carbonate, silicate and sulfide minerals of zinc. Also, the method is specific to copper pyritic ores, as well as to all thorium ores and minerals.

A further objective is to disclose the handling of ore treated. I have discovered that most gangue minerals such as silicates and sulfides of iron are unaffected by the collector of this invention. Hence, a method for ob taining a highly selective concentration of the desired metal values is provided.

BRIEF SUMMARY OF THE INVENTION This invention relates to a new and improved froth flotation method for recovering of minerals containing iron oxide ores as well as zinc minerals containing oxide, carbonate, silicate, and sulfide of zinc, by means of alkali or ammonium alkyl, alkylaryl, or aryl sulfinates as a new class of froth flotation reagents with promoting, collecting and frothing properties in a slightly acid or slightly alkaline pulp of mineral slurry.

The present invention points to a variety of compounds of nearly identical properties and behaviors in the froth flotation process of my invention, serving as collectors for iron oxide minerals i.e., hematite and magnetite in which iron is trivalent, and not for iron minerals in which the iron is divalent as in silicates, titanates, carbonates and sulfides. The feasibility of furnishing pure iron concentrates to the metallurgy is a big advantage of this invention. Namely, many iron ore deposits are mixed with iron silicate minerals and iron titanate minerals, because of which no pure and high grade concentrates can be obtained by ordinary meth ods and agents as yet known and practised. The alkyl, alkylaryl, and aryl sulfinic acids andtheir alkali and ammonium salts of this invention are specific to trivalent iron. Thus, all minerals with divalent iron are not responsive to the collector, the said sulfinates of this invention, so there ensues no levitation of such minerals as iron silicates and iron titanates.

This invention relates to the beneficiation of oxide iron ores, hematite and magnetite only. The essential iron ores of the present and future utilization, which at the same time are the most widely distributed and in certain places occurring in enormous quantities such as ferruginous quartzites, ferruginous chert or slats such as the taconite and itabirite. All such ores occur in the form of compact ferruginous siliceous rocks, in which the iron oxide is so finally disseminated that substantially all of the iron bearing particles of merchantable grade ore is smaller than 20 mesh. Those taconites and ferruginous quartzits which contain sufficient amounts of magnetite to demonstrate magnetic properties have been beneficiated magnetically to recover the magnetite content. The associated nonmagnetic hematite, however, has been discarded from these processes. Likewise, nonmagnetic taconite ores in which the iron is present as hematite have generally been unavailable as a source of iron even though they may contain larger proportions of iron than the magnetic taconites. Such ores are amenable to the beneficiation method of this invention.

Moreover, the widely distributed rocks containing substantial amounts of magnetite, ilmenite, some iron phosphates, as well as many of the ferruginous silicate minerals such as chlorite, biotite, epidote, pyroxenes and garnets, are unavailable as cheap and satisfactory source of iron concentrates because of the intolerable presence of titanium or phosphorous, or ferruginous silicates. All mentioned accessory minerals are not floatable with alkyl or aryl alkali or ammonium sulfinates. Thus the invented froth flotation reagents enlarge the availability of potential sources of iron ore.

Furthermore, the black sands and the beach sands are highly amenable to the flotation process of this invention. Besides being predominantly magnetite, the black sands contain ilmenite, rutile, sphene, zircon, monazite, garnet and often chromite as the most abundant accessory mineral ingredients of a given black sand. Of all these minerals, only the magnetite responds to the collectors to this invention, thus cromite, ilmenite, garnet as well as many other ferruginous and titaniferrous minerals of divalent iron do not respond to the applied collector. Zirconium, rare earth, earth alkali, aluminum minerals, silica and silicates do not respond to the flotation method of this invention. Thus the black sands and the beach sands represent an additional and cheap source of satisfactory iron concentrates, besides an appreciable amount of a mixed concentrate-tailings rich in titanium, zirconium, serium, rare earth and chromium minerals which are amenable to other selective froth flotation processes.

The present invention comprises a method for the beneficiation of iron oxide ores which comprises: comminuting the ore to liberate substantially all the iron oxide mineral from the gangue, and adding to the mineral slurry of the comminuted ore an alkali or ammonium alkyl, alkylaryl, or aryl sulfinate in a slightly acidic pulp of the said mineral slurry. Thus the hematite or magnetite minerals of the treated ore, in accordance with the invention, is rendered responsive to levitation from siliceous gangue and other heretofore minerals, accessory minereals, and is collected in the froth flotation process.

The special feature of this invention using alkyl, alkylaryl, or aryl ammonium sulfinates is in the nonfloating of minerals with divalent iron, i.e., the common sulfide of iron, such as pyrite, arsenopyrite and the like iron sulfides, also, ferromagnesian silicates and the like minerals, such as garnet, biotite, chlorite, hornblende, augite, forsterite, fayalite and the like minerals, as well as all alkalialuminum silicates and earthalkalialuminum silicates, calcite, dolomite, siderite, barite, and the like carbonate and sulfate minerals.

Furthermore, the zinc minerals of all kind are responsive to the alkali or ammonium alkyl and aryl sulfinates as collecting reagents of this invention. Thus, this invention relates to a new froth flotation method for the recovery of minerals containing zinc with alkali or ammonium alkyl or aryl sulfinates as a new class of flotation reagents. These reagents are particularly adapted for use in a highly selective method for recovering zinc minerals from their ores which contain lead and pyritic minerals, besides silica, calcite, dolomite, siderite, and barite.

The special feature of froth flotation procedure of zinc, copper, pyrite ores by means of alkali or ammonium, alkyl or aryl sulfinates instead of xanthates is distinguished by the elimination of activation of zinc minerals with copper sulfate and the flotation in a highly alkaline pulp of the mineral slurry in the zinc circuit, followed the flotation of copper mineral in low alkaline pulp. Thus, the present invention eliminates the high consumption of copper sulfate, soda ash and lime, as well as the thickening and pumping which obviously is a significant advantage. The reagent cost with application of alkali or ammonium aklyl or aryl sulfinates as flotation reagents is approximatelly half as high as the reagent cost with application of potassium alkyl xanthates as flotation reagents, besides that a frother is eliminated also, all of which represents an important saving.

The froth flotation collectors as defined herein are particularly effective in flotation processes used to separate and concentrate zinc sulfide from copper sulfide, pyrite and pyrrhotite after the lead is floated out with aerofloat from common lead-zinc sulfide ores. In such a process, a pulp is first prepared by wet grinding of a sulfide containing ore to a suitable particles zise, after which the pulp of the mineral slurry is subjected to froth flotation by means of aerofloat reagent in the presence of sodium cyanide, which collects the lead concentrate in the usual manner. This step finished, the elimination of galena, sulfuric acid is added to lower the pH value of the pulp of mineral slurry; then an effective amount of ammonium alkyl or aryl sulfinate as collector for zinc mineral is added, usually in an amount ranging from about 0.10 to about 0.25 lb/ton of the ore in the pulp of mineral slurry. The pulp is then agitated and aerated. The zinc sulfide mineral is collected in a conventional way where the froth is readily overflowed or skimmed off the residual gangue and nondesired materials. Thus the zinc metal value therein is recovered. But the flotation of zinc mineral may be floated first with a suitable sulfinate and the lead, copper, pyrite tailings subjected to conventional flowsheet for lead, copper, pyrite ores.

The flowsheet with application of ammonium alkyl or aryl sulfinates is shorter and more direct, which is a big technical advantage. The sulfinates have neither an unpleasant odor, nor are poisonous.

Furthermore, as will be seen from what follows, the time of flotation required is comparativelly short as compared to conventional flotation circuits with xanthate reagents. This not only means an appreciable sav- 5 ing in capital cost but also is an important reduction in operating costs.

The froth flotation process of this invention is best accomplished in an alkaline or slightly acid pulp of mineral slurry because the free sulfinic acid is more aggressive than its alkali and ammonium salts. But free acid decomposes and oxidizes quickly, therefore, it is held and added to the flotation circuit as alkali or ammonium salts which are quite stable. The pH of the flotation circuit is operative from 5 to 9. In spite of the wide range of the pH value the standard pH control technics are substantially unaffected in this process of my invention, and should be applied where needed in connection with the character of the particular ore treated and the ore pretreatment during the milling stage. The alkyl as well as the aryl sulfinate-mineral complexes of iron, zinc, copper, and thorium are unaffected by diluted alkaline or acidic mineral slurry under the conditions prevaling in the froth flotation practice. In any case, in slightly alkaline, neutral, or slightly acid pulp of mineral slurry there ensues the formation of the hydrophobic complex of alkyl or aryl sulfinates of iron, zinc, copper, and thorium minerals respectivelly. The characteristics of the process of this invention is the persistance of the promotion.

THE PREFERRED EMBODIMENTS According to the invention, valuable alkyl, aryl, and alkylaryl sulflnic acids and their salts, alkali and ammonium sulfinates respectively are provided and proved, of which the generic formula is:

R S 0.I'Ie

40 wherein R is a straight or branched alkyl chain of 2 to wherein R is ethane, propane, butane and the like low alkanes; or benzene, toluene, xylene, naphthalene; and Me is alkali metal or ammonia.

The alkyl, alkylaryl, and aryl sulflnic acids and their corresponding sulfinates of alkali metals and ammonia are water repellent and are wet with difficulty, because of this property they develop by itself the foaming and frothing properties under the conditions prevaling in the froth flotation process. In spite of a great many vari- Benzenedlsummm g O M eties of sulfinic acids they do not differ appreciably in Me. O g their general habit, i.e., collecting characteristics in 3 froth flotation process of this invention, of which sulfi- 5 nates several characteristics groups are presented here- CH O inbelow Toluenedisulfinate 3 5 O.Me I group of alkylsulfinates; wherein Me is alkali metal or o 1 ammonia. O

i Propanesuimate C(C: i 0 e Isopentanesulfinate (Cd5) (CI-I )5 0.11s

Octanesulfinate CH (C':E .S O.l e

Ethane-a1fa-beta-clisulfinate Pie-.0 s (cs: s 0.129

It 2 2 n O C II group of arylsulfinates and aryldisulfinates; wherein CH 3 Me is alkali metal or ammonia. xylenedlsumnm 5 0 Me Me. O a 0 Benzenesulfinate O.M 3o

III Group of aralkyl sulfinates of the generic formula:

Toluenesulfinate 3 9 S O.Me

I CH -CH I O.Me O R o Xylenesulflnate 3 ll 5 O.Me

wherein R is benzene, benzoic acid, salicylic acid, cres- 3 otinic acid; and Me is alkali metal or ammonia.

Phenylethanesulfinate Q-Cl-L-CH, i O.Me

Benzoic ethancsulfinate HOOBQ- CH,CH i O.Me

Salicylicethanesulfinate H0O CH,CH a O.Mc

Cresotinicethanesulfinate HOOC IV Group of aryloxysulfinate of the generic formula: V Group of carboxyaryl sulfinates of the generic formula:

v wherein R is benzoic acid, toluic acid, cinnamic acid,

wherein R is phenol, cresol, carbethoxyphenol, carbesalicylic acid, cresotinic acid; and Me is alkali metal or thoxycresol, anisol; and Me is alkali metal or ammonia. l0 ammonia.

Phenolsulfinate Cresolsulfinate Carbethoxyphenolsulfinate Carbethoxycresolsulfinate Anisolsulfinate ll Cinnamic(acid)sulfinate CH fH C OH (phenylacrylic acid) O O.Me

O u Salicylic(ucid)sulfinate c OH Me.O S H O 9 Cresotinic(acid)sulfinate c OH MeO- a VI Group of chloro-aryl sulfinates, chloro-nitro-aryl sulfinates of the generic formula:

wherein R is chlorobenzene, dichlorobenzene, chloronitrobenzene; and Me is alkali metal or ammonia.

-O.Me

l? Chlorohenzenesulflnate :5 O.Ml

O n Dichlorobenzenesulflnate s O-Me Cl C] Q O Chloro-nitrobenzenesulflnate n S O.Mo

Cl @NO VII Group of naphthalenesulfmate, naphthalenedisulfinate, tetrahydronaphthalenesulfinate.

THE GENERAL CONSIDERATION OF AMMONIUM ALKYL, ALKYLARYL AND ARYL SULFINATES THEIR POSSIBILITIES AS FROTH FLOTATION REAGENTS Very good results were obtained in the froth flotation examinations for iron oxide minerals, zinc minerals with alkali and ammonium alkyl, alkylaryl, and aryl sulfmates of the following constitution:

Iron minerals Ammonium octanesulfinate Ammonium benzenesulfinate Ammonium toluenesulfinate Ammonium benzenedisulfinate Ammonium phenylethanesulfinate Ammonium anisolsulfinate Ammonium carbethoxyphenolsulfinate Ammonium carbethoxycresolsulfinate Ammonium benzoic(acid)sulfinate Ammonium cinnamic(acid)sulfinate Ammonium salicyclic(acid)sulfonate Ammonium naphthalenesulfinate Ammoniumnaphthalenedisulfinate Ammonium tetrahydronaphthalenesulfinate Ammonium chlorobenzenesulfinate Ammonium dichlorobenzenesulfinate Ammonium chloro-nitrobenzenesulfinate Zinc minerals Ammonium ethanesulfinate Ammonium propanesulfinate Ammonium isopentanesulfinate Ammonium ethanedisulfinate Ammonium benzenesulfinate Ammonium toluenesulfmate Ammonium benzenedisulfinate Ammonium toluenedisulfinate Ammonium phenylethanesulfinate Ammonium naphthalenesulfinate Copper minerals Ammonium methylbenzenesulfinate Ammonium methylnaphthalenesulfinate Ammonium i-naphthalenesulfinate Ammonium nitronaphthalenesulfinate Thorium minerals Ammonium benzenesulfinate Nickel minerals Ammonium Z-naphtalenesulfinate From the above list of useful alkyl and aryl ammonium sulfinates it is evident that the alkyl as well as the aryl sulfinates are specific froth flotation reagents for iron minerals and zinc minerals.

The comparisons of recoveries of zinc metal values and iron metal values obtained from the respective ores are given the following Table. The recoveries were always very good, as well as the grade of concentrates obtained, which naturally depended on the grade of zinc mineral, i.e., the grade of zinc metal in respective minerals.

Zinc Iron recovery recovery Sulfonates percent percent Ammonium isopentanesulfinate 92.4 Ammonium ethanedisulfinate 89.8 Ammonium benzenesulfinate 91.6 91.2 Ammonium benzenedisulfinate 93.1 89.3 Ammonium octanesulfinate 92,8 Ammonium anisolsulfinate 90.0 Ammonium carhethoxyphenolsulfinate 88.4 Ammonium benzoic(acid)sulflnate 90.6 Ammonium salicylic(acid)sulfinate 91.1 Ammonium naphthalenesulfinate 92.6

The grade of iron concentrate were:

The highest the lowest Magnetite 66.3 62.l Hematite 64.0 60.4

The grade of copper concentrates were:

Chalcopyrite 28.4 Mixed copper ore 34.6

The above discussion as well as the disclosure illustrates my invention in a broad and general way; for a detailed illustration thereof the examples of the preferred embodiments of flotation practice are set forth below.

The procedure in performing the laboratory examples for iron, zinc, and copper ores was of the same manipulation as follows: The feed has been sized to pass 100 mesh standard sieve. Transfering the sized feed in the flotation machine, various amounts of said alkyl, alkylaryl, or aryl ammonium sulfinates and sulfuric acid were added. The pH of the pulp of mineral slurry was adjusted at 5 to 6; conditioned for 3 minutes, then aerated. The rougher concentrates were skimmed for 4 minutes. The rougher concentrates were cleaned with processed water.

The results of these flotation tests of iron ore are scheduled in the accompaning table.

In the same way the examinations were fulfilled with benzenesulfinate, benzenedisulfinate, anisolsulfinate, carbethoxyphenolsulfinate, benzoic(acid )sulfinate. The recoveries of iron obtained were in the range of general possibilities of sulfmates as froth flotation reagents for oxide iron minerals, i.e., hematite and magnetite. The success of concentration depends more on the nature of iron ore to be beneficiated and less on the reagents used.

10 The special feature of the herein defined froth flotation collectors is their selectively towards the zinc minerals. The affinity towards copper minerals and pyrite is nil with specific reagents for zinc minerals. Such a quality aids in the selective flotation of complex lead, zinc, copper, pyrite ores, and especially in cases of oxidized lead, zinc, copper, pyrite ores, or exclusively for oxide, carbonate or sulfate and silicate zinc ores. Thus residual sulflnic deposits with predominantly lean zinc mineral value, or otherwise unavailable tailings with some appreciable percentage of zinc metal value are amenable to the froth flotation with alkyl, alkylaryl, or aryl ammonium sulflnates of this invention.

In fulfilling the zinc sulfide flotation from a complex lead, zinc, copper, pyrite sulfide ore, the feed was com- In the flotation machine after reagentizing and without any conditioning the sample was aerated and the rougher zinc concentrate was skimmed for 10 minutes.

The results of the flotation tests of zinc ore are scheduled in the accompaning table:

The zinc mineral in the tested ore was a brown marmatite because no high grade zinc concentrate could be obtained. In the cleaner tailing appeared coarse grained brown-black marmatite with very little pyrite.

Ore Collector H 50, Assay of products treated pound per ton Feed Conc. Recovery Example 1 Ammonium octanesulflnate Fe Fe Fe Magnetite 0.3 0.2 Hematite 33.6 64.7 90.0

Example 2 Ammonium octanesulfinate Fe Fe 70 Fe 7:

the same 0.6 0.3

ore 33.6 64.9 92.8

Example 3 Ammonium salicylic(acid)sulfinate Specular 0.3 0.2 Fe Fe Fe hematite 31.2 64.0 91.]

Example 4 Ammonium naphthalenedisulfinate Fe 7c Fe Fe 0.2 0.2 Magnetite 28.2 66.3 92.6

Ore Collector H Assay of products treated pound per ton Feed Conc. Recovery Example I Ammonium isopentanesulfinate Zn 7!. Zn Zn 72 Lead,zinc, 0.3 02

copper. 8.62 52.8 93.1 pyrite ore Example 2 Ammonium benzenesulflnate Zn 7: Zn Zn 0.2 The same ore 8.62 50.4 90.6

In the same way, the examinations were fulfilled with ammonium benzenedisulfinate, ammonium ethanedisulfinate. The recoveries of zinc were in the range of general possibilities of alkyl and aryl sulfinate as froth flotation reagents for zinc minerals. The success of concentration depends more on the nature of the zinc ore to be beneficiated and less on the reagents used.

In all these investigations, no cleaning of the rougher concentrate were performed because of small amounts of rougher concentrates as well as of the cleaner tailings. lnvestigations at this point indicate that the faulty operating conditions were the very low densities under which the cleanings have to be performed, which produced great losses from produced concentrates to the cleaner tailings. So it became obvious that some thickening would have to be done before any successful treatment of this kind of cleaning and upgrading could be devised, which, obviously, could be done, only on a large scale.

The investigation of feasibility of froth flotation of copper minerals, performed with ammonium methylbenzenesulfinate (ammonium toluenesulfinate), was qualitative only. With nitronaphthalanesulfinate the investigation was quantitative. The recovery of copper metal value was as high as 90 percent, and the grade of concentrate was 28.4 percent of copper metal.

The investigations of feasibility of froth flotation of thorium minerals, performed with ammonium benzenesulfinate, was qualitative only, because of small quantity of thorium mineral. The recovery was obtained by microscopic count and was at 85 percent high. Coarse thorium was found in tailings.

The froth flotation of the present invention is carried out in accordance with good flotation practice and usually, though not always, involves flotation in rougher cells, followed by one or more cleanings of the rougher concentrate. The reagents are effective in small amounts and the promotion is sufficiently persistent so that it is feasible to carry out the rougher and cleaner flotation with a single addition of reagents at the begining of the operationv On the other hand, it is sometimes advantageous to use stage additions of reagents. Pulp densities are, in general, the same as in other applications of froth flotation practice, i.e., about 15 to percent of solids by weight.

The flotation plant practice by serving the alkyl, alkylaryl, and aryl alkali or ammonium sulfinate for the recovery of metal values, i.e., floating the aforesaid minerals of iron, zinc, copper, and thorium, the ore is crushed and sized to at least about 80 to 120 mesh standard sieve, which depends on the particular ore treated. Milling to finer sizes is preferable. It is also preferable to grind the iron ore with the addition of 2 pounds per ton of sulfuric acid for the cleaning the surface of quartz and silicate particles from adhered tiny films of iron oxide. If this procedure is applied the feed must be cycloned and washed to eliminate all soluble iron salts, which may be reagent consuming, and therefore deleterious. After this step the crushed and sized ore is pulped and as a mineral slurry is ready for the treatment in the flotation plant equipment, i.e., by passing through the conditioner where the collector and sulfuric acid are added. From the conditioner the pulp is pumped in the receiving box of the first stage or the main flotation bank. In the main flotation bank the froth produced by agitation is skimmed or is overflowed in the usual manner. In most cases it is advantageous to use multiple stage flotation processes to treat the underflow or partially metal value barren pulp to increase the degree of separation or to enhance the grade of recovery. Also, the use of varying amounts of emulsifiers, dispersants, and depressants etc. In different stages may be used to advantage to obtain the highest yield and best separation.

Having disclosed the novel collectors of this invention as well as the handling of the mineral slurry, l have to say the final objective of this invention is to provide a method for the flotation recovery of minerals containing iron, zinc, copper, and thorium.

From the foregoing, it will be seen that this invention is one well adapted to attain all of the ends and objects hereinabove set forth, thogether with other advantages which are obvious and which are inherent to the process and method.

It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims.

The invention having been described, what is claimed 1. A method of beneficiating ores selected from the group consisting of hematite, magnetite sulfide, sulfate, oxide, carbonate, and silicate of zinc; sulfide, carbonate, and silicate of copper; oxide and phosphate of thorium by froth flotation process to produce a froth concentrate of desired metal values leaving gangue miner als in tailings such as silica, alumino and ferromagnesian silicates, calcite, dolomite, siderite, barite, pyrite and pyritic minerals, which comprises effecting the froth flotation of the said ores and minerals in the presence of alkyl, alkylaryl, and aryl sulfinic promotercollectors, and their alkali metal and ammonium salts as prmoter-collectors, possessing some frothing properties, floating the desired metal values at a pH value of the flotation circuit from 5 to 9; and recovering a froth concentrate relatively rich in the desired metal value leaving a tailings relatively poor in the desired metal value.

2. A method according to claim 1, in which said collector is a sulfinate of which the generic formula is:

wherein R is selected from the group of straight or branched alkyl chain with 2 to 12 carbon atoms; or R is an aryl or alkylaryl compound such as benzene, toluene, xylene, phenol, cresol, carbethoxyphenol, carbethoxycresol, anisol (methoxyphenol), benzoic acid, phenylacetic acid, phenylacrylic(cinnamic) (cinnamic) acid, methylbenzoic(toluic) acid, hydroxybenzoic(salicylic) acid, hydroxytoluic(cresylic or cresotinic) acid, diphenylglycole, naphthalene, tetrahydronaphthalene, chlorobenzene, dichlorobenzene, chloro-nitrobenzene; and wherein Me is hydrogen, alkali metal, or ammonia.

3. A method according to claim 1, in which said collector is a disulfinate of which the generic formula is:

.vherein R is selected from the group of straight alkyl chain of low alkane such as ethane, propane, butane;

or R is an aryl compound such as benzene, toluene, xylene, naphthalene; and wherein Me is hydrogen, alkali metal, or ammonia.

4. A method according to claim 1, of beneficiating hematite and magnetite ores to produce a froth concentrate of high grade iron metal value, which comprises effecting froth flotation of said ore at apH from to 9 of the pulp of mineral slurry in the presence of alkyl, alkylaryl, or aryl ammoniumsulfinate, wherein said alkyl, alkylaryl, or aryl radical R is defined as in claim 2; and recovering a high grade iron froth concentrate, leaving a silica, and silicate tailings poor in iron metal value.

5. A method according to claim 1, of beneficiating zinc sulfide, sulfate, oxide, carbonate, and silicate ores occuring in complex lead, zinc, copper, pyrite sulfide ores, or their oxidized products to produce a froth concentrate of high grade zinc metal value which comprises effecting froth flotation of zinc sulfide, sulfate, oxide, carbonate, or silicate ore at a pH of 5 to 9 of the pulp of mineral slurry in the presence of alkyl, alkylaryl, or aryl ammonium sulfinate, wherein said alkyl,

alkylaryl, or aryl radical R is defined as in claim 2; and recovering a high grade zinc froth concentrate, leaving a silica, silicate, and sulfide tailings poor in zinc metal value.

6. A method according to claim 1, of beneficiating copper sulfide, carbonate, or silicate ores to produce a froth concentrate of high grade copper metal value which comprises effecting both flotation of the copper sulfide, carbonate, or silicate ore at a pH of 5 to 9 of the pulp of mineral slurry in the presence of said alkyl, alkylaryl, or aryl ammonium sulfinate, wherein alkyl, alkylaryl, or aryl radical R is defined as in claim 2; and recovering a high grade copper froth concentrate, leaving a pyrite, silica tailings poor in copper metal value.

7. A method according to claim 1, of beneficiating thorium oxide or phosphate minerals to produce a froth concentrate of high grade thorium metal value, which comprises effecting froth flotation of thorium mineral at a pH of 5 to 9 of the pulp of mineral slurry in the presence of ammonium benzenesulfinate; and recovering a high grade thorium froth concentrate, leaving a silica and silicate tailings poor in thorium metal value. 

1. A METHOD OF BENEFICIATING ORES SELECTED FROM THE GROUP CONSISTING OF HERMATITE, MAGNETITE SULFIDE, SULFATE, OXIDE, CARBONATE, AND SILICATE OF ZINC; SULFIDE, CARBONATE, AND SILICATE OF COPPER; OXIDE AND PHOSPHATE OF THORIUM BY FROTH FLOTATION PROCESS TO PRODUCE A FROTH CONCENTRATE OF DESIRED METAL VALUES LEAVING GANGUE MINERALS IN TAILINGS SUCH AS SILICA, ALUMINO AND FERROMAGNESIAN SILICATES, CALCITE, DOLOMITE, SIDERITE, BARITE, PYRITE AND PYRITIC MINERALS, WHICH COMPRISES EFFECTING THE FROTH FLOTATION OF THE SAID ORES AND MINERALS IN THE PRESENCE OF ALKYL, ALKYLARYL, AND ARYL SULFINIC PROMOTER-COLLECTORS, AND THEIR ALKALI METAL AND AMMONIUM SALTS AS PRMOTER-COLLECTORS, POSSESSING SOME FROTHING PROPERTIES, FLOATING THE DESIRED METAL VALUES AT A PH VALUE OF THE FLOTATION CIRCUIT FROM 5 TO 9; AND RECOVERING A FROTH CONCENTRATE RELATIVELY RICH IN THE DESIRED METAL VALUE LEAVING A TAILINGS RELATIVELY POOR IN THE DESIRED METAL VALUE.
 2. A method according to claim 1, in which said collector is a sulfinate of which the generic formula is:
 3. A method according to claim 1, in which said collector is a disulfinate of which the generic formula is:
 4. A method according to claim 1, of beneficiating hematite and magnetite ores to produce a froth concentrate of high grade iron metal value, which comprises effecting froth flotation of said ore at a pH from 5 to 9 of the pulp of mineral slurry in the presence of alkyl, alkylaryl, or aryl ammoniumsulfinate, wherein said alkyl, alkylaryl, or aryl radical R is defined as in claim 2; and recovering a high grade iron froth concentrate, leaving a silica, and silicate tailings poor in iron metal value.
 5. A method according to claim 1, of beneficiating zinc sulfide, sulfate, oxide, carbonate, and silicate ores occuring in complex lead, zinc, copper, pyrite sulfide ores, or their oxidized products to produce a froth concentrate of high grade zinc metal value which comprises effecting froth flotation of zinc sulfide, sulfate, oxide, carbonate, or silicate ore at a pH of 5 to 9 of the pulp of mineral slurry in the presence of alkyl, alkylaryl, or aryl ammonium sulfinate, wherein said alkyl, alkylaryl, or aryl radical R is defined as in claim 2; and recovering a high grade zinc froth concentrate, leaving a silica, silicate, and sulfide tailings poor in zinc metal value.
 6. A method according to claim 1, of beneficiating copper sulfide, carbonate, or silicate ores to produce a froth concentrate of high grade copper metal value which comprises effecting both flotation of the copper sulfide, carbonate, or silicate ore at a pH of 5 to 9 of the pulp of mineral slurry in the presence of said alkyl, alkylaryl, or aryl ammonium sulfinate, wherein alkyl, alkylaryl, or aryl radical R is defined as in claim 2; and recovering a high grade copper froth concentrate, leaving a pyrite, silica tailings poor in copper metal value.
 7. A method according to claim 1, of beneficiating thorium oxide or phosphate minerals to produce a froth concentrate of high grade thorium metal value, which comprises effecting froth flotation of thorium mineral at a pH of 5 to 9 of the pulp of mineral slurry in the presence of ammonium benzenesulfinate; and recovering a high grade thorium froth concentrate, leaving a silica and silicate tailings poor in thorium metal value. 